Search results for "Dissociation"
showing 10 items of 531 documents
Decay pathway determination of even-size dicationic silver clusters: Ag162+ and Ag182+ revisited by pre-precursor selection and sequential decay
2000
Abstract It is demonstrated how by selection of pre-precursor cluster ions Ag 2 n +1 2+ and collision-induced dissociation an ensemble of Ag 2 n 2+ can be produced, which is not contaminated by Ag n + clusters of the same size-to-charge state ratio, n / z . By use of this technique, Ag 16 2+ and Ag 18 2+ precursor ensembles have been prepared for further investigations. They are observed to decay by neutral monomer evaporation, Ag 2 n 2+ →Ag 2 n −1 2+ +Ag, and trimer fission, Ag 2 n 2+ →Ag 2 n −3 + +Ag 3 + , and show no sign of symmetric fission.
Monolayer Formation of Molybdenum Carbonyl on Cu(111) Revealed by Scanning Tunneling Microscopy and Density Functional Theory
2012
International audience; Molybdenum carbonyl Mo(CO)(6) was adsorbed on the Cu(111) surface at 160 K in the monolayer coverage range and studied by scanning tunneling microscopy. A well-ordered monolayer of hexacarbonyl molecules was observed experimentally for the first time. The monolayer has a hexagonal structure compatible with a (root 7 x root 7)R19 superlattice on the copper (111) plane. The arrangement and orientation of the molecules on the surface were determined by density functional theory calculations, including van der Waals interactions. The comparison of adsorption and cohesive energies reveals that the molecule-substrate interaction is stronger than the intermolecular one, whi…
Ligand dynamics of tert-butyl isocyanide oxido complexes of molybdenum(IV).
2014
The six-coordinate molybdenum(IV) oxido isocyanide complex 1 [Δ,Λ-OC-6-2-3-[MoO(N(p)∩N(i))2(CN(t)Bu)]; N(p)∩N(i) = 4-tert-butylphenyl(pyrrolato-2-ylmethylene)amine] is obtained in diastereomerically pure form in the solid state, as revealed by single-crystal X-ray diffraction. In solution, this stereoisomer equilibrates with the Δ,Λ-OC-6-2-4 diastereomer 2 at ambient temperature. The stereochemistry of both isomers has been elucidated by NMR, IR, and UV/vis spectroscopy in combination with density functional theory (DFT)/polarizable continuum model and time-dependent DFT calculations. The isomerization 1 → 2 is suggested to proceed via a dissociative trigonal twist with dissociation of the …
Solution and solid state studies with the bis-oxalato building block [Cr(pyim)(C2O4)2]− [pyim = 2-(2′-pyridyl)imidazole]
2013
The preparation, X-ray structure, and variable temperature magnetic study of the new compound {Ba(H2O)3/2[Cr(pyim)(C2O4)2]2}n·9/2nH2O (1) [pyim = 2-(2′-pyridyl)imidazole and C2O42− = dianion of oxalic acid], together with the potentiometric and spectrophotometric studies of the protonation/deprotonation equilibria of the pyim ligand and the ternary complex [Cr(pyim)(C2O4)2]−, are reported herein. The crystal structure of 1 consists of neutral chains, with diamond-shaped units sharing barium(II), with the two other corners occupied by chromium(III). The two metal centers are connected through bis(bidentate) oxalate. Very weak antiferromagnetic interactions between the chromium(III) ions occu…
Selected dissociation‐ and correlation‐consistent configuration interaction by a perturbative criterion
1990
We propose a perturbative criterion to select the most important dissociation‐ or correlation‐consistent type of contributions to perform generalized valence bond‐configuration interaction (GVB‐CI) calculations, dissociation‐consistent configuration interaction (DCCI) or correlation‐consistent configuration interaction (CCCI) approach, respectively. The procedure presented is computationally less demanding than the CCCI proposed by Goddard and co‐workers. To ensure the distance consistency of the MOs used, the nonvalence virtual orbitals are obtained by a projection technique. The results obtained for a few test calculations show the ability of the suggested approach to get close results to…
The molecular dynamics of thermoreversible networks as studied by broadband dielectric spectroscopy
1995
Polybutadienes modified by a small number of 4-phenyl-1,2,4-triazoline-3,5-dione form thermoreversible networks via hydrogen bonding between the polar stickers. The molecular dynamics of systems with different contents of polar stickers are investigated by broadband dielectric spectroscopy in the frequency regime of 10−1–109 Hz. Unmodified polybutadiene shows two relaxation processes, the α-relaxation which is correlated to the dynamic glass transition of the polybutadiene, and a β-relaxation corresponding to a local relaxation of polybutadiene segments. In the polar functionalized systems, besides these two relaxations, an additional relaxation process (called α*) is observed, which occurs…
Measurement of the inelastic proton-proton cross-section at √s = 7 TeV with the ATLAS detector
2011
The dependence of the rate of proton–proton interactions on the centre-of-mass collision energy, √s, is of fundamental importance for both hadron collider physics and particle astrophysics. The dependence cannot yet be calculated from first principles; therefore, experimental measurements are needed. Here we present the first measurement of the inelastic proton–proton interaction cross-section at a centre-of-mass energy, √s, of 7 TeV using the ATLAS detector at the Large Hadron Collider. Events are selected by requiring hits on scintillation counters mounted in the forward region of the detector. An inelastic cross-section of 60.3±2.1 mb is measured for ξ>5×10[superscript −6], where ξ is ca…
Spatiotemporal reaction kinetics of an ultrafast photoreaction pathway visualized by time-resolved liquid x-ray diffraction.
2006
We have studied the reaction dynamics for HgI 2 in methanol by using time-resolved x-ray diffraction (TRXD). Although numerous time-resolved spectroscopic studies have provided ample information about the early dynamics of HgI 2 , a comprehensive reaction mechanism in the solution phase spanning from picoseconds up to microseconds has been lacking. Here we show that TRXD can provide this information directly and quantitatively. Picosecond optical pulses triggered the dissociation of HgI 2 , and 100-ps-long x-ray pulses from a synchrotron probed the evolving structures over a wide temporal range. To theoretically explain the diffracted intensities, the structural signal from the solute, the…
Los fenómenos disociativos: una revisión conceptual
2003
En el presente trabajo se lleva a cabo una revisión del concepto de disociación y de los fenómenos asociados, haciendo un recorrido desde las posturas clásicas, como la de Janet, hasta los planteamientos que actualmente se centran en el estudio de los fenómenos disociativos. Se aborda, además el planteamiento acerca de la existencia de un continuo de experiencias disociativas, o modelo dimensional, que actualmente se formula conjugado con un modelo tipológico, y se hace una breve revisión de los estudios que se han centrado en las relaciones entre la variable disociación y ciertas variables que tradicionalmente han sido asociadas a este concepto, como la hipnotizabilidad o la represión. Fin…
A diffusion model account of normal and impaired readers.
2004
Acquired aphasics and dyslexics with even very profound word reading impairments have been shown to perform relatively well on the lexical decision task (e.g., Buchanan, Hildebrandt, & MacKinnon, 1999), but direct contrasts with unimpaired participants data is often complicated by extremely long reaction times for patient data. The dissociation between lexical decision and word naming performance shown by these patients is of theoretical importance, and here we present an analysis of processing underlying the lexical decision task. We are able to determine what aspects of performance are affected by acquired aphasics in the lexical decision task. We fit lexical decision data from aphasic pa…