Search results for "Delocalized electron"
showing 10 items of 158 documents
Electronic structure of MgO-supported Au clusters: quantum dots probed by scanning tunneling microscopy.
2007
We investigate via density functional theory (DFT) the appearance of small MgO-supported gold clusters with 8 to 20 atoms in a scanning tunneling microscope (STM) experiment. Comparison of simulations of ultrathin films on a metal support with a bulk MgO leads to similar results for the cluster properties relevant for STM. Simulated STM pictures show the delocalized states of the cluster rather than the atomic structure. This finding is due to the presence of s- derived delocalized states of the cluster near the Fermi energy. The properties of theses states can be understood from a jellium model for monovalent gold.
Intramolecular charge delocalization and nonlinear optical properties of Methyl 3-(4-methoxy phenyl) prop-2-enoate from vibrational spectra
2005
The density functional computations of MMP are performed at B3LYP/6-31G (d,p) level to derive equilibrium geometry, vibrational wavenumbers and intensities, and first hyperpolarizability. Large NLO efficiency predicted for the first time in this new class of compounds has been confirmed by powder efficiency experiments. DFT calculation reveals that endocyclic angle at the junction of the propenoate group and the phenyl ring is decreased from 120° by 2.5°, whereas two neighbouring angles around the ring are increased by 2.1° and 1.2° respectively, associated with intramolecular charge transfer interaction. The vibrational spectra confirm the charge transfer interaction between -COOCH3 group…
Molecular design of the diketopyrrolopyrrole-based dyes with varied donor units for efficient dye-sensitized solar cells
2014
Abstract Three types of novel diketopyrrolopyrrole-based organic dyes ( Type 1 – 3 ) with phenyl unit as an additional π -bridge and triphenylamine or phenothiazine as the donors are designed and synthesized for dye-sensitized solar cells (DSSCs). Type 1 dyes incorporating the donor segment directly to the diketopyrrolopyrrole core lead to a better electron communication between the donor and acceptor, allowing an efficient charge transfer process. Type 2 and Type 3 dyes with a phenyl unit between the donor and diketopyrrolopyrrole unit show lower delocalization of the excited state. Compared with Type 3 dyes, Type 1 dyes exhibit higher conjugated skeleton co planarity and shorter electron …
Delocalized Nature of theEδ′Center in Amorphous Silicon Dioxide
2005
We report an experimental study by electron paramagnetic resonance (EPR) of E(')(delta) point defect induced by gamma-ray irradiation in amorphous SiO2. We obtained an estimation of the intensity of the 10 mT doublet characterizing the EPR spectrum of such a defect arising from hyperfine interaction of the unpaired electron with a 29Si (I=1/2) nucleus. Moreover, determining the intensity ratio between this hyperfine doublet and the main resonance line of E(')(delta) center, we pointed out that the unpaired electron wave function of this center is actually delocalized over four nearly equivalent silicon atoms.
SUBWAVELENGTH OPTICAL DEVICES FOR NANOMETER SCALE APPLICATIONS
2002
Recent progress in near-field optics instrumentation led to a new class of subwavelength optical experiments in which it is intended to use either the optical tunnel effect (OTE) or the lower mode based transmission (LMBT) in order to control the optical transfer between several delocalized detection or injection centers. This paper presents a panel of new theoretical and experimental results computed or observed near various dielectric or metallic patterns, linear, curved, or dashed, integrated in coplanar geometry. In particular, we demonstrate, how an efficient control of light evanescent waves can allow structures of subwavelength cross sections to be addressed.
Asymmetry and Non-Adiabaticity in Fragmentation of Disulfide Bonds upon Electron Capture
2010
Although it has been generally assumed that electron attachment to disulfide derivatives leads to a systematic and significant activation of the S-S bond, we show, by using [CH(3)SSX] (X = CH(3), NH(2), OH, F) derivatives as model compounds, that this is the case only when the X substituents have low electronegativity. Through the use of MP2, QCI and CASPT2 molecular orbital (MO) methods, we elucidate, for the first time, the mechanisms that lead to unimolecular fragmentation of disulfide derivatives after electron attachment. Our theoretical scrutiny indicates that these mechanisms are more intricate than assumed in previous studies. The most stable products, from a thermodynamic viewpoint…
Conformational and structural studies of N-methylacetohydroxamic acid and of its mono- and bis-chelated uranium(VI) complexes
2015
The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.86(2) and 9.63(5) for NMAH and NMA(-), respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemic…
On the Structure of Thiolate-Protected Au25
2008
Density functional theory is used to explore the structure of Au25(RS)18. The preferred structure consists of an icosahedral Au13 core protected by 6 RS-Au-RS-Au-RS units. The enhanced stability of the structure as an anion is found to originate from closure of an eight-electron shell for delocalized Au(6s) electrons. The evaluated XRD pattern and optical spectra are in good agreement with experimental data.
The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster
2010
The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic co…
Synthesis, molecular and electronic structures of a paramagnetic trimetallic cluster containing an unusual Mo3(μ3-Se)2(μ-Se)3 core
2014
Abstract The electron precise [Mo3(μ3-Se)(μ-Se)3(dppe)3Br3]+ incomplete cuboidal complex, with six cluster skeletal electrons (CSE), was converted into the paramagnetic bicapped [Mo3(μ3-Se)2(μ-Se)3(dppe)3]+ cluster (1+), with an unusual seven metal electron population, by treatment with elemental Ga. The cluster core consists of an almost equilateral Mo3 triangle (Mo–Mo distances are in the range 2.7583(7)–2.7748(7) A with an average value of 2.77(3) A), capped by two selenide ligands. The remaining selenium atoms bridge adjacent metal atoms, defining a virtually planar Mo3(μ-Se)3 unit, with the capping Se atoms positioned above and below this plane. The new complex possesses a doublet grou…