Search results for "State"
showing 10 items of 9165 documents
Unveiling the high reactivity of cyclohexynes in [3 + 2] cycloaddition reactions through the molecular electron density theory
2018
[3 + 2] cycloaddition (32CA) reactions of cyclohexyne, a cyclic strained acetylene, with methyl azide and methoxycarbonyl diazomethane have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d) computational level. These 32CA reactions, which take place through a one-step mechanism involving highly asynchronous transition state structures, proceed with relatively low activation enthalpies of 6.0 and 4.3 kcal mol-1, respectively, both reactions being strongly exothermic. The reactions are initiated by the creation of a pseudoradical center at one of the two acetylenic carbons of cyclohexyne with a very low energy cost, 1.0 kcal mol-1, which promotes the eas…
Cobaltocenium substituents as electron acceptors in photosynthetic model dyads
2017
Abstract Cobaltocenium carboxylic acid hexafluorophosphate has been attached to a zinc(II) meso-tetraphenyl porphyrin chromophore via an amide linkage. Optical and electrochemical studies reveal that the metallocene and the porphyrin interact only negligibly in the ground state of the dyad. Photoinduced charge-shift from the zinc porphyrin to the cobaltocenium substituent to give the zinc porphyrin radical cation and the cobaltocene occurs upon exciting the porphyrin with light. Steady state emission, time-resolved fluorescence and transient absorption pump–probe spectroscopy in addition to density functional theory calculations suggest that the charge shift to the cobaltocenium substituent…
Photo-Chromium: Sensitizer for Visible-Light-Induced Oxidative C−H Bond Functionalization-Electron or Energy Transfer?
2017
The chromium(III) sensitizer [Cr(ddpd)2]3+ - based on an earth-abundant metal center - possesses a unique excited state potential energy landscape (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). The very large energy gap between the redox active and substitutionally labile 4T2 state and the long-lived low-energy 2E spin-flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron transfer pathways from the ultrashort-lived excited 4T2 state. This specific excited state reactivity enables a …
Synthesis and solid state structure for a series of poly(1-pyrrolylmethyl)benzene derivatives. Control of the interplaying π–π and C–H⋯π interactions?
2006
The syntheses of new hexa- and 1,2,4,5-tetra-1-pyrrolylmethyl-benzene (1 and 2, respectively) compounds and their crystal structures, along with those for the related disubstituted o-, m- and p-di-1-pyrrolylmethyl-benzene (3–5) derivatives are reported. The arrangements of molecules in the 1-D structure for 2–5 are controlled by the interplay of two different weak interactions: π–π and C–H⋯π (Ph) interactions. The absence of such interactions in the packing of 1 seems to be related to the arrangement of the pyrrolylmethyl arms with respect to the benzene core, which prevents the π cloud of the aromatic ring to be part of any intermolecular interaction. In addition, C–H⋯π (pyrrolyl) interact…
Encapsulation of tetramethylphosphonium cations
2009
International audience; The weak interactions and capsule formation of tetramethylphosphonium (TMP) cation with resorcinarenes 1 and 2 and the corresponding pyrogallarenes 3 and 4 were studied in the solid state by single crystal X-ray diffraction, in solution by NMR and in the gas phase by mass spectrometry. In methanol-D4, the NMR titration studies reveal that the association constants for the 1:1 complexes of TMP@3 and TMP@4 are much higher (TMP@4:390±37 M-1) than for the corresponding TMP@1 and TMP@2 (TMP@2:130±10 M-1) complexes. In the gas phase both monomeric 1:1 TMP@1-TMP@4 complexes as well as the dimeric 1:2 capsule complexes, TMP@12-TMP@42 were observed. The 1:1:2 molar mixtures o…
Theoretical investigation of the spin crossover transition states of the addition of methane to a series of Group 6 metallocenes using minimum energy…
2016
International audience; Density functional calculations are reported on the addition of methane to Group 6 metallocenes, M(η-C5H5)2 (M), M(CH2(η-C5H4)2) (a-M) and M(η-C5Me5)2 (M*) where M = Mo and W. Full geometry optimisations were carried out on the singlet and triplet 16 electron complexes, 1[M] and 3[M], the η2-methane complexes, 1[M(η2-CH4)], and the hydridomethyl adducts, 1[M(CH3)(H)]. The triplet state for [M] was found to be more stable for all six metallocenes, the difference being least in the case of the ansa-bridged system. Formation of the hydridomethyl complexes was exoenergetic for all tungsten systems and for a-Mo, the other two Mo systems being endoenergetic. Minumum energy…
The WISE 2000 and 2001 Field Experiments in Support of the SMOS Mission:Sea Surface L-Band Brightness Temperature Observations and Their Application …
2004
Camps, Adriano ... et al.-- 20 pages, 16 figures, 3 tables
The global forest above-ground biomass pool for 2010 estimated from high-resolution satellite observations
2021
Funding Information: We are thankful to the GlobBiomass project team and Frank Martin Seifert (ESA) for valuable suggestions and stimulating scientific discussions. We are thankful to Takeo Tadono (JAXA EORC), Masato Hayashi, (JAXA EORC), Kazufumi Kobayashi (RESTEC), Åke Rosenqvist (soloEO), and Josef Kellndorfer (EBD) for support with the use and interpretation of the ALOS PALSAR mosaics. Support by the CCI Land Cover project team, in particular Sophie Bontemps (UCL), is greatly acknowledged. The help from Martin Jung (MPI-BGC) in feature selection and Ulrich Weber (MPI-BGC) for data processing for the GSV-to-AGB conversions is greatly acknowledged. Forest inventory data for the validation…
Inter-annual climate variability in Europe during the Oligocene icehouse
2017
Abstract New sclerochronological data suggest that a variability comparable to the North Atlantic Oscillation (NAO) was already present during the middle Oligocene, about 20 Myr earlier than formerly assumed. Annual increment width data of long-lived marine bivalves of Oligocene (30–25 Ma) strata from Central Europe revealed a distinct quasi-decadal climate variability modulated on 2–12 (mainly 3–7) year cycles. As in many other modern bivalves, these periodic changes in shell growth were most likely related to changes in primary productivity, which in turn, were coupled to atmospheric circulation patterns. Stable carbon isotope values of the shells (δ 13 C shell ) further corroborated the …
Modelling and Analysis of Flow Rate and Pressure Head in Pipelines
2019
Currently, various approaches with several utilities are proposed to identify damage in the pipeline. The pipeline system is modeled in the form of a distributed parameter system, such that the state space related to the distributed parameter system contains infinite dimension. In this paper, a novel technique is proposed to analyze and model the flow in the pipeline. Important theorems are proposed for testing the observability as well as controllability of the proposed model.