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Cheng W Kuthirummal N Gosselin JL Sølling TI Weinkauf R Weber PM 《The journal of physical chemistry. A》2005,109(9):1920-1925
Local photoionization pathways and charge-transfer dynamics of 2-phenylethyl-N,N-dimethylamine (PENNA) are explored using the recently developed Rydberg fingerprint spectroscopy. PENNA, a molecule that derives its biological significance from its relation to neurotransmitters, has two ionization centers that are separated by an ethyl group. We ionize the molecule in various multiphoton ionization processes using different laser wavelengths. The Rydberg fingerprint spectrum reveals the local nature of the ionization process and identifies the center of charge. We discovered that the laser wavelength provides substantial control over the activation of the individual ionization centers. The resonant (2+1) ionization with 400-nm radiation is dominated by the ejection of an electron from the amine moiety. In contrast, the resonant (1+1) ionization with 266-nm radiation leads predominantly to an ion with the charge in the phenyl group. The clean separation of the two ionization processes allows the exploration of ultrafast charge-transfer dynamics ensuing from a specific starting state characterized by a charged phenyl moiety. The width of the corresponding spectral features suggests that the charge transfer proceeds on a femtosecond time scale, suggesting a strong coupling between the two lowest-energy electronic surfaces of the PENNA cation. 相似文献
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The infrared absorption spectra of glycine silver nitrate (GAgNO3) and glycine nitrate (GHNO3) show that the glycine group exists completely in the zwitter ion form in the former and in both forms in the latter. The spectrum of GAgNO3 at liquid air temperature did not reveal any striking change which can be attributed to a freezing of the rapid reorientation of the NH 3 + group taking place at higher temperatures. The position of the COO? stretching frequencies indicate that this group is co-ordinated only weakly to the Ag+ ion. The summation frequencies reported by Schroeder, Wier and Lippincott (1962) for AgNO3 were not observed in the present study on GAgNO3. It shows however that ferroelectricity in GAgNO3 is in all probability due to the motion of the Ag+ ion in the oxygen co-ordination polyhedron and is not directly connected with the ordering of the hydrogen bonds below Curie point. 相似文献
97.
In this contribution, we have studied structural and photophysical properties of aggregated CdS quantum dots (QDs) capped with 2-mercaptoethanol in aqueous medium. The hydrodynamic diameter of the nanostructures in aqueous solution was found to be approximately 160 nm with the dynamic light scattering (DLS) technique, which is in close agreement with atomic force microscopy (AFM) studies (diameter approximately 150 nm). However, the UV-vis absorption spectroscopy, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM) studies confirm the average particle size (QD) in the nanoaggregate to be 4.0 +/- 0.5 nm. The steady-state and time-resolved photoluminescence studies on the QDs further confirm preservation of electronic band structure of the QDs in the nanoaggregate. To study the nature of the nanoaggregate we have used small fluorescent probes, which are widely used as biomolecular ligands (2,6-p-toluidinonaphthalene sulfonate (TNS) and Oxazine 1), and found the pores of the aggregate to be hydrophobic in nature. The significantly large spectral overlap of the host quantum dots (donor) with that of the guest fluorescent probe Oxazine 1 (acceptor) allows us to carry out F?rster resonance energy transfer (FRET) studies to estimate average donor-acceptor distance in the nanostructure, found to be approximately 25 Angstrom. The quantum dot aggregate and the characterization techniques reported here could have implications in the future application of the QD-nanoaggregate as host of small ligand molecules of biological interest. 相似文献
98.
The need to design proton-conducting electrolytes for fuel cells operating at temperatures of 120 degrees C and above has prompted the investigation of various "water-free" polymeric materials. The present study investigates the properties of "water-free" proton-conducting membranes prepared from high-molecular-weight polymeric organic amine salts. Specifically, the properties of bisulfates and dihydrogenphosphates of poly-2-vinylpyridine (P2VP), poly-4-vinylpyridine (P4VP), and polyvinylimidazoline (PVI) have been investigated over the temperature range of 25-180 degrees C. Nanocomposites of these polymeric organic amine salts and hydroxylated silica have also been investigated in this study. These polymers are found to be stable and proton-conducting at temperatures up to 200 degrees C. In all the polymer examples studied herein, the phosphates are more conducting than the bisulfates. The activation energy for ionic conduction was found to decrease with increasing temperature, and this is associated with the increased polymer mobility and ionization of the proton. This is confirmed by the high degree of motional narrowing that is observed in proton NMR experiments. The measured values of conductivity and the differences in pKa values of the polymeric organic amine and the mineral acid are clearly correlated. This observation provides the basis for the design of other water-free acid-base polymer systems with enhanced proton conductivity. The results presented here suggest that anhydrous polymer systems based on acid-base polymer salts could be combined with short-range proton conductors such as nanoparticulate silica to achieve acceptable conductivity over the entire temperature range. 相似文献
99.
This paper describes the preparation and conductivity studies of polyindole–ZnO composite polymer electrolyte (CPE) with LiClO4. Polyindole–ZnO-based polymer nanocomposites were prepared by chemical method and characterized by XRD, infrared (IR), scanning
electron microscope (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The IR spectrum confirms
the intermolecular interaction between polyindole and ZnO. The significant spectral changes of polyindole and ZnO nancomposites
reveal the strong interaction between polyindole and ZnO nanoparticles. The structural morphologies of the ZnO, polyindole,
and polyindole–ZnO are obtained from SEM. The TEM image of polyindole nanocomposite shows that ZnO is embedded in polyindole
matrix. An enhanced conductivity of 4.405 × 10−7 S cm−1 at 50 °C for the CPE was determined from impedance studies. 相似文献
100.
A conic integer program is an integer programming problem with conic constraints. Many problems in finance, engineering, statistical
learning, and probabilistic optimization are modeled using conic constraints. Here we study mixed-integer sets defined by
second-order conic constraints. We introduce general-purpose cuts for conic mixed-integer programming based on polyhedral
conic substructures of second-order conic sets. These cuts can be readily incorporated in branch-and-bound algorithms that
solve either second-order conic programming or linear programming relaxations of conic integer programs at the nodes of the
branch-and-bound tree. Central to our approach is a reformulation of the second-order conic constraints with polyhedral second-order
conic constraints in a higher dimensional space. In this representation the cuts we develop are linear, even though they are
nonlinear in the original space of variables. This feature leads to a computationally efficient implementation of nonlinear
cuts for conic mixed-integer programming. The reformulation also allows the use of polyhedral methods for conic integer programming.
We report computational results on solving unstructured second-order conic mixed-integer problems as well as mean–variance
capital budgeting problems and least-squares estimation problems with binary inputs. Our computational experiments show that
conic mixed-integer rounding cuts are very effective in reducing the integrality gap of continuous relaxations of conic mixed-integer
programs and, hence, improving their solvability.
This research has been supported, in part, by Grant # DMI0700203 from the National Science Foundation. 相似文献