Multiphoton ionization and ab initio calculation studies of pyridine-water mixed clusters using time of flight mass spectrometer

Multiphoton ionization of binary mixed clusters (C5H5N)(x)-(H2O)(y) at 532, 355 and 266 nm laser wavelengths has been investigated using TOF mass spectrometer. The experiments showed that almost all the products were protonated ions, At 532 and 355 nm, the products were mainly protonated pyridine clusters (C5H5N)(n)-H+, while at 266 nm, mixed binary cluster ions (C5H5N)(m)- (H2O)(n)-H+ appeared. It was found that the abundance of the [(C5H5N)(3)-H2O-H](+) ions was abnormally high. The calculation indicated that the ion [(C5H5N)(3)-H2O-H](+) is Of a kind of magic number structures with C-3v symmetry. A stepwise reaction mechanism is suggested that photoionization is followed by dissociation. (C) 2001 Elsevier Science B.V. All rights reserved.

Chemical Bonding and Electronic Structure of 4d-Metal Monosulfides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. The calculated bond distance decreases with the increasing of atomic number of 4d metals, reaches minimum at RhS, then increases. For cationic molecules, the calculated bond distance decreases to the minimum at MoS+, then increases. The calculated vibrational frequency decreases from YS(YS+) to PdS(PdS+) for both neutral and cationic molecules. The bond ionic character decreases from YS(YS+) to PdS(PdS+) for neutral and cationic molecules. The bonding patterns are discussed and compared with the available studies.

Electronic structure of interfaces between copper-hexadecafluoro-phthalocyanine and 2,5-bis(4-biphenylyl) bithiophene

The interfaces formed between copper-hexadecafluoro-phthalocyanine (F16CuPc) and 2,5-bis(4-biphenylyl) bithiophene (BP2T) were examined using photoemission and inverse photoemission spectroscopy. It is observed that in F16CuPc/BP2T the heterojunction is characterized by band bending in both materials, while in BP2T/F16CuPc the band bending is confined in BP2T only. The combination of the band bending and finite Debye lengths provides an explanation to the observed ambipolar behavior of the organic thin film transistors based on such heterojunctions.

Interfacial electronic structure of copper phthalocyanine and copper hexadecafluorophthalocyanine studied by photoemission

Electronic structures of the heterojunction between copper phthalocyanine (CuPc) and copper hexadecafluorophthalocyanine (F16CuPc) were studied with ultraviolet photoemission spectroscopy. Band bending and an interface dipole were observed at the interface due to the formation of an electron accumulation layer and a depletion layer in F16CuPc and CuPc, respectively. Such an energy level alignment leads to interesting ambipolar characteristics for application of the CuPc/F16CuPc junction in organic field-effect transistors.

Chemical bonding and electronic structure of 4d-metal monocarbides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. For neutral and cationic molecules, the bond distance decreases from YC (YC+) to RhC (RhC+), then increases, while for anionic molecules, the bond distance decreases from YC- to RuC-, then increases. Opposite trend was observed for vibrational frequency. The bond ionic character decreases from ZrC to PdC for neutral molecules. The bonding patterns are discussed and compared with the available studies.

Substitution effect of nitrogen atoms with carbon atoms in porphyrin on the electronic structure and excited states properties

Density functional theory (DFT) electronic structure calculations were carried out to predict the structures and the absorption and emission spectra for porphyrin and a series of carbaporphyrins-carbaporphyrin, adj-dicarbaporphyrin, opp-dicarbaporphyrin, tricarbaporphyrin and tetracarbaporphyrin. The ground- and excited-state geometries were optimized at the B3LYP/6-31g(d) and CIS/6-31g(d) level, respectively. The optimized ground-state geometry and absorption spectra of porphyrin, calculated by DFT and time-dependent DFT (TDDFT), are comparable with the available experimental values. Based on the optimized excited-state geometries obtained by CIS/6-31g(d) method, the emission properties are calculated using TDDFT method at the B3LYP/6-31g(d) level. The effects of the substitution of nitrogen atoms with carbon atoms at the center positions of porphyrin are discussed. The results indicate that the two-pyrrole nitrogens are important to the chemical and physical properties for porphyrin.

Synthesis, extraction and electronic structure of Ce@C-2n

In view of the growing interest in endohedral lanthanide fullerenes, Ce, as a typical +4 oxidation state lanthanide element, has been systematically studied. The synthesis, extraction and electronic structure of Ce@C-2n are investigated. Soot containing Ce@C-2n was synthesized in high yield by carbonizing CeO2-containing graphite rods and are back-burning the CeC2-enriched cathode deposit in a DC are plasma apparatus. Ce@C-2n, dominated by Ce@C-82, can be efficiently extracted from the insoluble part of the soot after toluene Soxhlet extraction by pyridine at high temperature and high pressure in a closed vessel. About 60% Ce@C-2n (2n = 82,80,78,76) and 35% Ce@C-82 can be enriched in the pyridine extract. This fact is identified by desorption electron impact mass spectrometry (DEI MS). The electronic structure of Ce@C-2n is analyzed by using X-ray photoemission spectroscopy (XPS) of pyridine-free film. It is suggested that the encapsulated Ce atom is in a charge state close to +3 and was effectively protected from reaction with water and oxygen by the enclosing fullerene cage. Unlike theoretical expectation, the electronic state of Ce@C-82 is formally described as Ce+3@C-82(3-). (C) 1997 Elsevier Science Ltd.

Ab initio study on the interaction of La (III) with adrenaline

The interaction of La(III) with adrenaline was studied using Ab initio method. The geometry of the complex of La (III) with adrenaline was optimized, and the La(III) bonding site in adrenaline was ascertained.

ELECTRONIC-STRUCTURE AND CHEMICAL BONDING OF EUROPIUM NITRATE COMPLEX WITH AZACROWN (2, 2)

The electronic structure and bond character of europium nitrate complex with azacrown (2, 2)(1, 7, 10, 16-tetraoxa-4, 13-diazacyclooctadecane), [Eu(NO_3)_2(2, 2)] NO_3, have been studied by means of XPS and INDO method. The data of electronic binding energies and charge distribution of atoms in the complex showed that chemical shift of less electronegative nitrogen N1s binding energy was larger than that of more electronegative oxygen O1s binding energy in coordinating atoms, and that charge transfer from N...