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541.
542.
Benkö G Myllyperkiö P Pan J Yartsev AP Sundström V 《Journal of the American Chemical Society》2003,125(5):1118-1119
Photoinduced electron injection from the sensitizer Ru(dcbpy)2(NCS)2 (RuN3) into SnO2 and TiO2 nanocrystalline films occurs by two distinct channels on the femto- and picosecond time scales. The faster electron injection into the conduction band of the different semiconductors originates from the initially excited singlet state of RuN3, and occurs in competition with intersystem crossing. The rate of singlet electron injection is faster to TiO2 (1/55 fs-1) than to SnO2 (1/145 fs-1), in agreement with higher density of conduction band acceptor states in the former semiconductor. As a result of competition between the ultrafast processes, for TiO2 singlet, whereas for SnO2 triplet electron injection is dominant. Electron injection from the triplet state is nonexponential and can be fitted with time constants ranging from approximately 1 ps (2.5 ps for SnO2) to approximately 50 ps for both semiconductors. The major part of triplet injection is independent of the semiconductor and is most likely controlled by intramolecular dynamics in RuN3. The overall time scale and the yield of electron injection to the two semiconductors are very similar, suggesting that processes other than electron injection are responsible for the difference in efficiencies of solar cells made of these materials. 相似文献
543.
Kárpáti T Veszprémi T Thirupathi N Liu X Wang Z Ellern A Nyulászi L Verkade JG 《Journal of the American Chemical Society》2006,128(5):1500-1512
The synthesis and the crystal and molecular structure of N(CH(2)CH(2)NMe)(3)P=CH(2) is reported. The P-N(ax) distance is rather long in N(CH(2)CH(2)NMe)(3)P=CH(2). The ylide N(CH(2)CH(2)NMe)(3)P=CH(2) proved to be a stronger proton acceptor than proazaphosphatrane N(CH(2)CH(2)NMe)(3)P, since it was shown to deprotonate N(CH(2)CH(2)NMe)(3)PH(+). The extremely strong basicity of the ylide is in accordance with its low ionization energy (6.3 eV), which is the lowest in the presently investigated series N(CH(2)CH(2)NMe)(3)P=E (E: CH(2), NH, lone pair, O and S), and to the best of our knowledge it is the smallest value observed for a non-conjugated phosphorus ylide. Computations reveal the existence of two bond strech isomers, and the stabilization of the phosphorus centered cation by electron donation from the equatorial and the axial nitrogens. Similar stabilizing effects operate in the case of protonation of E. A fine balance of these different interactions determines the P-N(ax) distance, which is thus very sensitive to the level of the theory applied. According to the quantum mechanical calculations, methyl substitution at the equatorial nitrogens flattens the pyramidality of this atom, increasing its electron donor capability. As a consequence, the PN(ax) distance in the short-transannular bonded protonated systems and the radical cations is longer by about 0.5 A in the N(eq)(Me) than in the N(eq)(H) systems. Accordingly, isodesmic reaction energies show that a stabilization of about 25 and 10 kcal/mol is attributable to the formation of the transannular bond in case of N(eq)(H) and the experimentally realizable N(eq)(Me) species, respectively. 相似文献
544.
545.
Westenhoff S Beenken WJ Friend RH Greenham NC Yartsev A Sundström V 《Physical review letters》2006,97(16):166804
In isolated conjugated polymers two explanations are in discussion for the redshift of the emission on a picosecond time scale-exciton energy transfer (EET) between conjugated segments along the chains and conformational changes of these segments themselves, i.e., torsional relaxation. In order to resolve this question we perform femtosecond time-resolved transient absorption measurements of the energy relaxation of poly[3-(2,5-dioctylphenyl)thiophene] in toluene solution. We show that torsional relaxation can be distinguished from EET by site-selectively exciting low-energy conjugated segments. We present a unified model that integrates EET and torsional dynamics. In particular, comparison to ultrafast depolarization measurements shows that torsional dynamics cannot be neglected when analyzing EET dynamics and furthermore reveals that the exciton extends itself by about 2 monomer units during torsional relaxation. 相似文献
546.
Gayou O Aniol KA Averett T Benmokhtar F Bertozzi W Bimbot L Brash EJ Calarco JR Cavata C Chai Z Chang CC Chang T Chen JP Chudakov E De Leo R Dieterich S Endres R Epstein MB Escoffier S Fissum KG Fonvieille H Frullani S Gao J Garibaldi F Gilad S Gilman R Glamazdin A Glashausser C Gomez J Gorbenko V Hansen JO Higinbotham DW Huber GM Iodice M de Jager CW Jiang X Jones MK Kelly JJ Khandaker M Kozlov A Kramer KM Kumbartzki G LeRose JJ Lhuillier D Lindgren RA Liyanage N Lolos GJ Margaziotis DJ 《Physical review letters》2002,88(9):092301
The ratio of the electric and magnetic form factors of the proton G(E(p))/G(M(p)), which is an image of its charge and magnetization distributions, was measured at the Thomas Jefferson National Accelerator Facility (JLab) using the recoil polarization technique. The ratio of the form factors is directly proportional to the ratio of the transverse to longitudinal components of the polarization of the recoil proton in the elastic e(-->)p---> e(-->)p reaction. The new data presented span the range 3.5< Q(2)< 5.6 GeV(2) and are well described by a linear Q(2) fit. Also, the ratio sqrt[Q(2)] F(2(p))/F(1(p)) reaches a constant value above Q(2) = 2 GeV(2). 相似文献
547.
We describe a transition from fully synchronous periodic oscillations to partially synchronous quasiperiodic dynamics in ensembles of identical oscillators with all-to-all coupling that nonlinearly depends on the generalized order parameters. We present an analytically solvable model that predicts a regime where the mean field does not entrain individual oscillators, but has a frequency incommensurate to theirs. The self-organized onset of quasiperiodicity is illustrated with Landau-Stuart oscillators and a Josephson junction array with a nonlinear coupling. 相似文献
548.
An ability to analyze the geometrodynamic degrees of freedom and initial-data formulation is central to the canonical quantization of gravity. In the metric theory of gravity York provided the most powerful technique to analyze the dynamic degrees of freedom and to solve the initial-data problem. In this paper we extend York's analysis to tetrad gravity. Such an extension is necessary for the quantization of gravity when coupled to a half-integer-spin field. We present a comparative analysis of the geometric information carried by (1) a 3-metric of an initial hypersurface and (2) the spacelike triad of a time-gauged tetrad. We apply the tetrad initial-data formulation to Ashtekar's connection variables, and provide a comparison with other alternative choices of canonical tetrad variables. 相似文献
549.
Norman W. Gilman Betty C. Holland R. Ian Fryer 《Journal of heterocyclic chemistry》1977,14(7):1163-1169
The syntheses of novel 8-chloropyrazolo[1,5-a][1,4]benzodiazepines and of an imidazo-benzodiazepinone utilizing products from the nucleophilic substitution of fluorine in 2-fluoro-5-nitrobenzophenone ( 1 ) by pyrazole-3,5-dicarboxylic acid, dimethyl ester ( 2 ) and by 2-methyl-imidazole-4,5-dicarboxylic acid, diethyl ester ( 30 ) are described. 相似文献