Search results for "Physics::Chemical Physics"
showing 10 items of 517 documents
Phase transitions and quantum effects in adsorbed monolayers
1996
Phase transitions in absorbed (two-dimensional) fluids and in absorbed layers of linear molecules are studied with a combination of path integral Monte Carlo (PIMC), Gibbs ensemble Monte Carlo (GEMC), and finite size scaling techniques. For a classical (nonadditive) hard-disk fluid the “critical” nonadditivities, where the entropy-driven phase separations set in, are presented. For a fluid with internal quantum states the gas-liquid coexistence region, tricritical, and triple points can be determined, and a comparison with density functional (DFT) results shows good agreement for the freezing densities. LinearN 2 molecules adsorbed on graphite (in the √3 × √3 structure) show a transition fr…
Mesoscopic gels at low agarose concentration: perturbation effects of ethanol
1997
Aqueous agarose solutions at low concentrations (0.5 g/liter) were temperature quenched below the spinodal line to form mutually disconnected mesoscopic gels. In the presence of 6% ethanol, these solutions, obtained by quenching at the same temperature depth as in pure water, appear much more fluid, as determined by probe diffusion experiments. We show by static and dynamic light scattering that this can be explained by the solvent-mediated effects of ethanol, leading to a globular shape of mesoscopic agarose gels, rather than to an extended rodlike structure observed in pure water. Our findings show the significant effects of solvent perturbations on particle condensation and, therefore, m…
Chalcogen adsorption and surface magnetism
2000
Abstract Investigations concerning the electronic and magnetic properties of oxygen and sulfur adsorbed on magnetized surfaces were carried out by means of angle and spin resolving photoelectron spectroscopy. Iron(110), a polycrystalline iron alloy, and an amorphous metallic glass (Fe 79 B 16 Si 5 ) served as ferromagnetic substrates. Exchange splittings of the O 2p and S 3p derived levels could be detected, demonstrating a magnetic coupling between the chemisorbate and iron. This observation presents a prerequisite for an induced magnetic moment within the adsorbate overlayer. For sulfur an adsorbate-induced structure only in the minority spin channel near the Fermi level was observed whic…
Rotation of methyl radicals in molecular solids.
2010
Electron spin resonance (ESR) measurements were carried out to study the rotation of methyl radicals (CH(3)) in solid carbon monoxide, carbon dioxide, and nitrogen matrices. The radicals were produced by dissociating methane by plasma bursts generated by a focused 193 nm ArF excimer laser radiation during the gas condensation on the substrate. The ESR spectra exhibit anisotropic features that persist over the temperature range examined, and in most cases this indicates a restriction of rotation about the C(2) symmetry axis. A nonrotating CH(3) was also observed in a CO(2) matrix. The intensity ratio between the symmetric (A) and antisymmetric (E) nuclear spin states was recorded as a functi…
Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces
2015
Surface enhanced Raman spectra from molecules (bipyridyl ethylene) adsorbed on gold dumbells are observed to become increasingly asymmetric (Fano-like) at higher incident light intensity. The electronic temperature (inferred from the anti-Stokes (AS) electronic Raman signal increases at the same time while no vibrational AS scattering is seen. These observations are analyzed by assuming that the molecule-metal coupling contains an intensity dependent contribution (resulting from light-induced charge transfer transitions as well as renormalization of the molecule metal tunneling barrier). We find that interference between vibrational and electronic inelastic scattering routes is possible in …
Reorientational dynamics in simple supercooled liquids
1998
Abstract The geometry of the reorientational dynamics in the van der Waals liquid, toluene, and the hydrogen bond network, glycerol, are compared. Both systems have contributions from small angle fluctuations. In glycerol the fraction of these small angle fluctuations is much larger than in toluene, due to the stronger anisotropic interactions in the former substance. The average reorientational angle in both systems is similar and on the order of 10 ∘ . In addition we analyze the stretching of the rotational correlation functions of rank one and two. In both cases we find that the second rank correlation function has a more pronounced stretching than the corresponding first rank correlatio…
Relaxation of certain integral functionals depending on strain and chemical composition
2012
We provide a relaxation result in $BV \times L^q$, $1\leq q < +\infty$ as a first step towards the analysis of thermochemical equilibria.
Models of SHS: An overview
2007
International audience; The theoretical models of SHS based on lamellar or cellular approximations of the heterogeneous reactive media are comparatively analyzed. It is shown that the ratio of the reaction time to the characteristic time of heat transfer between particles is a decisive parameter for the combustion wave propagation. When the time of reaction is shorter than the time of heat exchange, the combustion occurs in a discrete mode; in the opposite case, a quasi-homogeneous combustion mode occurs. Development of the discrete cellular model does not discard the quasi-homogeneous approach but markedly extends the scope of combustion theory. This extension enables explanation of many o…
A simple analysis of the HA centre destruction temperatures for doped alkali halides
1998
Abstract A simple relation for the destruction temperatures Td of the HA centres (H centres trapped by an impurity cation) as a function of the difference in the radii for a host cation and impurity in alkali halide crystals is presented and theoretically justified. This relation allows to predict Td for H centres trapped by other monovalent cation impurities.
Rotational Relaxation of Nitrogen in Ternary Mixtures N2-CO2-H2O - Consequences in Coherent Anti-Stokes-Raman Spectroscopy Thermometry
1991
0021-9606; The influence of CO2 and H2O on the rotational relaxation processes of N2 in ternary mixtures N2-CO2-H2O is investigated. The efficiency of these perturbers is responsible for significant modifications of the state-to-state relaxation rates and broadening coefficients. Flame data are well reproduced by taking into account these modifications. The role of these minor species in the determination of temperatures in premixed flames is analyzed. The present relaxation model allows us to understand why the discrepancy between observed and calculated coherent anti-Stokes Raman spectroscopy (CARS) spectra in flames is sometimes resolved by empirically adding a dephasing component to pur…