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排序方式: 共有309条查询结果,搜索用时 15 毫秒
1.
Pop D Winter B Freyer W Widdra W Hertel IV 《The journal of physical chemistry. B》2005,109(16):7826-7833
Photoemission measurements were performed on a series of stepwise benzoannelated zinc porphyrazine molecules in thin films. The electronic structure of tert-butyl-substituted zinc tetraazaporphyrin, phthalocyanine, and naphthalocyanine is investigated using mainly EUV synchrotron radiation. A detailed analysis of the zinc satellites in the spectra of the valence region is performed in an attempt to infer the effect of ligand size extension on the metal-ligand interactions. No differences in the character of the bond between zinc and ligand were detected as a function of ligand size. The results are compared with those for the respective metal-free and copper-containing molecules. 相似文献
2.
The structure of the title compound has been determined by X-ray crystallography. The octahedral arrangement of ligands about the iron(II) centre is somewhat distorted, with the axial NC–Fe–CN bond angle being 174.3(4)°. The oxidation of the tricyano-2,2,6,2- terpyridylferrate(II) anion by the peroxodisulfate anion has been investigated in water and in binary aqueous mixtures. The reaction follows a second order rate law, with a second-order rate constant of 0.126± 0.001dm3mol–1s–1 at 295.2K. The enthalpy and entropy of activation in water are 51.3±1.8kJmol–1 and –89±5JK–1mol–1 respectively. The rate is retarded on addition of organic cosolvent. The transfer chemical potential of the initial state from water into mixed solvents has been determined from solubility measurements, and compared with the transfer potential of the transition state. Solvent effects on the reaction are discussed in terms of initial state versus transition state solvation. 相似文献
3.
J. C. Greer R. Ahlrichs I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(4):413-426
A theoretical study of the energetics and intramolecular dynamics for ammonia cluster cations (NH3) 2 + and (NH3) 3 + is presented. The proton transfer mechanism after a vertical ionisation is followed in detail. Structural and energetic calculations are performed near the Hartree-Fock self consistent field (HF-SCF) limit; all open shell calculations are spin restricted (RHF). The calculations reconcile experimental results from thermochemical and photoionisation measurements: discrepancies in the energetics are shown to be due to the probing of different regions of the potential energy surface (PES). For the dynamics calculations, it is impractical to determine a large region of the multidimensional PES and then integrate Newton's equations. The calculations therefore incorporate a quantum mechanical determination of the electronic energy of the system after each time increment while nuclear degrees of freedom are handled classically. In this way, the classical reaction path across the Born-Oppenheimer surface is obtained. 相似文献
4.
A. Bähring E. Meyer I. V. Hertel H. Schmidt 《Zeitschrift für Physik A Hadrons and Nuclei》1985,320(1):141-149
Pronounced polarization effects have been observed in inelastic collisions of laser state-prepared Na*(3p,M L) with Na+ leading to Na*(3d) for the energy rangeE CM=20–45 eV. Using linearly polarized light the dependence of the inelastic process on the alignment of the electronic charge cloud of the Na*(3p) prior to the collision has been measured. In studies with left and right hand circularly polarized light the angular momentum transferred in the collision process has been determined. The results are compared with similar data for the 3p→3s deexitation process studied previously [6]. The density matrix of the Na*(3p) state has been evaluated with respect to the collisional excitation to Na*(3d). Semiclassical calculations based on the coupled channel impact parameter approximation using pseudopotentials [7] and nonadiabatic rotational coupling elements for the Na 2 * system [12] have been performed. The agreement with the experimental results is good, in particular for the higher collision energies. 相似文献
5.
Alexander Goerke Gregor Leipelt Hartmut Palm C. P. Schulz I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,32(4):311-320
The first reactive differential scattering study for atomic clusters is reported. Oxidation of Na
x
(x8) with O2 is investigated in a crossed beam apparatus. Sodium oxide (Na
n
O,n4) and sodium dioxide (Na
n
O2,n6) are produced with a total reactive cross section from 50 to 80 Å2, depending on the cluster size. The excess energies for these reactions are estimated by an SCF type ab initio calculation and range from 0.5 to 5 eV. The large cross section may then be understood quantitatively in terms of a harpooning mechanism as a first step in the reaction path. Angular distributions have been determined for the most abundant products, showing strong forward scattering. Two different schemes are discussed for the reaction: while the dioxides Na
n
O2 may be formed by an evaporative cooling process from a highly excited collision complex, formation of Na
n
O appears to originate from a direct process. In both cases the experimental data suggest that most of the exothermicity remains in the reaction products. 相似文献
6.
E. E. B. Campbell R. R. Schneider A. Hielscher A. Tittes R. Ehlich I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,22(2):521-527
The collisional velocity dependence of the cross sections for fragmentation of mass-selected (CO2) n + (n+2...7) clusters in collisions with Ar atoms is presented. Interesting structure can be observed in the cross sections which indicate that the collision occurs between the Ar atom and one CO2 molecule within the cluster. The results may be explained by assuming that the collision leads to either vibrational excitation of a loosely bound CO2 monomer which then leaves the cluster or excitation of the entire cluster to a dissociative state. 相似文献
7.
8.
J. C. Greer C. Hüglin I. V. Hertel R. Ahlrichs 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1994,30(1):69-75
Geometric structures and the energies for the ground and several excited electronic states of a sodium atom bound with one or two ammonia molecules are presented. All self consistent field (SCF) calculations are performed with extended basis sets. Geometry optimization and one electron properties have been performed within the SCF approximation. Excited states have been calculated with the multi-configuration SCF (MCSCF) technique. This system may be viewed as a precursor to solvation in a macroscopic system. The excited state calculations provide important information for spectroscopic studies of these complexes. 相似文献
9.
Th. Freudenberg W. Radloff H. -H. Ritze V. Stert K. Weyers F. Noack I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1996,36(3-4):349-364
The formation of protonated and unprotonated ammonia cluster ions is studied by femtosecond two colour two photon pump-probe techniques applied to (NH3) n and (ND3) n clusters withn up to 8. The fourth harmonic (~ 200 nm, 6.2 eV, 160 fs) of a Ti: Sapphire laser pulse is used to excite the clusters in a state corresponding to theà state of NH3 while the third harmonic (267 nm, 4.65 eV) is used for the subsequent ionisation step. Employing a combination of the optical Bloch equations for the excitation process and rate equations for the cluster dynamics we calibrate the zero time delay and carefully analyse the time dependence of the pump-probe signal. Several distinct intermediate steps in the time evolution can be distinguished, having characteristic time constants ranging from 40 fs to over 100 ps. They are discussed in a consistent scheme for the excitation, ionisation and protonation dynamics, accounting also for characteristic differences observed between deuterated and undeuterated species. A particularly remarkable time dependence of the homogeneous (NH3) 2 + cluster ion signal is interpreted as a fingerprint of internally protonated neutral precursors of the type NH3NH2NH4. 相似文献
10.
Samoylova E Lippert H Ullrich S Hertel IV Radloff W Schultz T 《Journal of the American Chemical Society》2005,127(6):1782-1786
The excited-state dynamics of adenine and thymine dimers and the adenine-thymine base pair were investigated by femtosecond pump-probe ionization spectroscopy with excitation wavelengths of 250-272 nm. The base pairs showed a characteristic ultrafast decay of the initially excited pi pi* state to an n pi* state (lifetime tau(pi pi*) approximately 100 fs) followed by a slower decay of the latter with tau(n pi*) approximately 0.9 ps for (adenine)2, tau(n pi*) = 6-9 ps for (thymine)2, and tau(n pi*) approximately 2.4 ps for the adenine-thymine base pair. In the adenine dimer, a competing decay of the pi pi* state via the pi sigma* state greatly suppressed the n pi* state signals. Similarities of the excited-state decay parameters in the isolated bases and the base pairs suggest an intramonomer relaxation mechanism in the base pairs. 相似文献